Double-layer effects on simple electrode reactions III. The reduction of Eu3+ and Cr3+ in the presence of thiocyanate anions. Evidence for ligand bridging

The rates of reduction of Eu³⁺ and Cr³⁺ have been measured in mixed perchlorate + thiocyanate electrolytes at constant ionic strength, using low concentrations of thiocyanate to minimize its association with the cationic reactants. The effect of adsorbed thiocyanate anions on the reduction kinetics of Cr³⁺ resembled those produced by iodide and bromide on both Cr³⁺ and Eu³⁺. However, thiocyanate exhibited an unusual catalytic effect on the reduction of Eu³⁺ which was identified as arising from a reaction pathway involving thiocyanate-bridging between the mercury surface and the Eu³⁺. The diagnostic criteria used to support the proposed mechanism included analysis of the rate—potential behavior and of the effects of competitively adsorbed iodide ions upon the reduction rates.     

Metallacycloalkanes: I. Preparation and characterisation of α,α′-bipyridyl-5-nickela-3,3,7,7-tetramethyl-trans-tricyclo[4.1.0.02,4]heptane

Oxidative addition of 2 molecules of 3,3-dimethylcyclopropene (I) to α,α′-bipyridyl(1,5-cyclooctadiene)nickel(0) (III) gave the title compound (IV) in over 90% yield. Complex IV was characterized by mass, ¹H NMR and ¹³C NMR spectroscopy. Its structure was determined by X-ray diffraction (a 13.7081(2), b 14.638(2), c 9.5139(1) Å, β 110.82(1)°, C2/c, R = 0.05 for 1614 reflections).     

Bistable ferroelectric liquid crystal photoswitch triggered by a dithienylethene dopant

The spontaneous polarization (PS) of a ferroelectric liquid crystal is modulated reversibly by photocyclization of the dopant 1,2-bis[5'-(4' '-heptyloxyphenyl)-2'-methylthien-3'-yl]perfluorocyclopentene. The magnitude of PS photomodulation increases with dopant concentration up to 3 mol %, and the resulting photoswitch is fatigue resistant and bistable. To the best of our knowledge, this is the first example of a bistable ferroelectric liquid crystal photoswitch to be reported in the literature.     

Molecular potential-energy surfaces for chemical reaction dynamics

This paper reviews the construction of molecular potential-energy surfaces by an interpolation method which has been developed over the last several years. The method uses ab initio quantum chemistry calculations of the molecular electronic energy in an automated procedure to construct global potential- energy surfaces which can be used to simulate chemical reactions with either classical or quantum dynamics. The methodology is explained and several applications are presented to illustrate the approach. Received: 22 February 2002 / Accepted: 2 May 2002 / Published online: 6 November 2002 Correspondence to: M. A. Collins e-mail: collins@rsc.anu.edu.au Acknowledgements. The methods described in this overview are the result of collaborations with former members of my group, in particular with Josef Ischtwan, Meredith Jordon, Keiran Thompson and Ryan Bettens. I am also indebted for inspiration gained from many discussions with my colleagues Leo Radom and Donghui Zhang (National University of Singapore). This work has been supported by the Supercomputer Facility of the Australian National University and the Australian Partnership for Advanced Computing.     

Polystyrene resins with immobilized polyamines: Preparation,characterization, and ability to bind Cu(II) ions

Three polyamine ligands, ethylenediamine (EDA), diethylenetriamine (DTA), and triethylenetetramine (TETA), were bound to three chloromethylated “popcorn” polystyrene resins (16, 50, and 100% phenyl ring substitution) with the use of pyridine as the reaction medium. The rate of chloride displacement decreased with increasing molecular weight of the amine and higher degree of resin chloromethylation, while the extent of multiple attachments to the polymer matrix increased. The additional crosslinking, a result of multiple attachments, caused the polyamine resins to swell to a lesser extent in pyridine and water. The ability of the insoluble polyamine–polystyrene resins to chelate Cu²⁺ ions from dilute solutions (200 ppm) was determined at pH 5. With EDA resins the capacity for Cu²⁺ increased with increasing amount of the bound polyamine, with DTA it remained unchanged, while with TETA it was found to decrease.     

Zur Kenntnis der thermischen Zersetzung von Ammoniumhexafluoroscandat,-titanat,-vanadat und-chromat

Thermal analysis supported by kinetic calculations was applied exhaustively to these compounds. Under dynamic conditions, tetrafluorometallates(III), which as intermediates, could not be isolated, for the first three compounds. In each case, the final step was the pure metal(III) fluoride. Ammonium hexafluorochromate(III) decomposed directly to the pure chromium(III) fluoride. The decomposition rate of all compounds slowed down towards the end, probably for kinetic reasons. Polymorphic transitions of ammonium hexafluorotitanate(III) were observed at 35 and 100°C. Ammoniumhexafluoroscandate(III) underwent polymorphic transition at 47°C. The decomposition patterns for all these compounds were similar. Conditions for the preparation of pure ammonium tetrafluorometallates(III) of Sc, Ti and V are described.     

Marine adhesives. IV: Hexosamine content of Balanus eburneus adhesive

The adhesive secreted by the barnacle, Balanus eburneus, has been demonstrated to contain two hexosamines, glucosamine and galactosamine. Degradation of the hexosamines during hydrolysis of the adhesive appears to be the reason why previous studies of the adhesive have indicated the absence of hexosamines, or the presence of only one hexosamine.     

Polarographic reduction of pyridinium ion in pyridine tetraethylammonium perchlorate as background electrolyte

Tetraethylammonium perchlorate, compared to lithium perchlorate as background electrolyte for the reduction of pyridinium ion in pyridine, is effective over a wider potential range, but is more difficult to obtain in a pure state; slight amounts of impurities do not, however, affect the pyridinium wave. The pyridinium wave produced in 0.1 M Et₄NClO₄ may occur at a more negative potential than the main pyridinium wave in 0.1 M LiClO₄, depending on the source of the pyridinium ion, but still appears to be due to a diffusion-controlled reduction, whose limiting current is linearly proportional to concentration; the prewave observed in LiCl0₄ background generally does not appear in Et₄NClO₄ background. Specific differences in the effect of Li(I), Na(I) and Et₄N(I) background cation appear to be due to electrocapillary phenomena and perhaps to the extent of solvation of the ions. The constancy of current for solutions containing acetic acid with added acetate, pyridinium nitrate with added nitrate, and benzoic acid with added benzoate indicate that the pyridinium reduction is independent of anion concentration.     

Computational study on the ring-opening reaction of protonated oxirane and methylpropene

A computational study on the intermolecular reaction of protonated oxirane with methylpropene, as a model for initiation of oxidosqualene cyclisation, shows that the S_N2-like ring opening is strongly exothermic with a low barrier to reaction and establishes the geometry of the intermolecular reaction.